CN105854945B - A kind of storage-stable platiniferous hydrosilylation catalyst and preparation method thereof - Google Patents
A kind of storage-stable platiniferous hydrosilylation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105854945B CN105854945B CN201610221439.6A CN201610221439A CN105854945B CN 105854945 B CN105854945 B CN 105854945B CN 201610221439 A CN201610221439 A CN 201610221439A CN 105854945 B CN105854945 B CN 105854945B
- Authority
- CN
- China
- Prior art keywords
- storage
- stable
- hydrosilylation catalyst
- preparation
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- -1 Oxygen alkane Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229910019032 PtCl2 Inorganic materials 0.000 claims description 2
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical class C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/60—Groups characterized by their function
Abstract
The invention belongs to chemosynthesis technical field, specifically discloses a kind of storage-stable platiniferous hydrosilylation catalyst and preparation method thereof.The catalyst is formed after metal platinum organic complex and is added a certain amount of organic compound and be prepared by compound containing platinum and the ligand reaction of organosiloxane containing double bond；Wherein described organic compound is the compound with structure shown in formula I：
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of storage-stable platiniferous hydrosilylation catalyst and
Its preparation method.
Background technology
Hydrosilylation refers to what is carried out under certain condition with unsaturated compound by the silane compound of siliceous hydrogen
A kind of addition reaction, it is had a wide range of applications among organosilicon chemistry and consequence, since the reaction be found with
Come, in decades, experienced the development in faster several stages, reacted, arrived from the initial simple condition for using high temperature
Introduce the custom catalystses such as ultraviolet, peroxide, azo-compound afterwards to be catalyzed, until Speier discoveries, by chlorine platinum
Acid be dissolved in isopropanol can effective catalyzing addition reaction of silicon with hydrogen, platinum element is incorporated into hydrosilylation for the first time.This
Willing reacts chloroplatinic acid and silicone compounds containing unsaturated bond on the basis of the method that Speier is used afterwards, will be anti-
The compound that should be formed afterwards is used in hydrosilylation, can continue to improve the efficiency of Si―H addition reaction.Karstedt is in forefathers
On the basis of, Willing method is further improved, using chloroplatinic acid or chloroplatinate in ethanol with sodium acid carbonate and
Vinylsiloxane heating response, form the vinylsiloxane complex compound of platinum, such a catalyst for eliminating halogen, catalysis effect
For rate compared with the vinylsiloxane complex compound of chloroplatinic acid before, its catalytic efficiency has further raising, such a catalysis
Agent is still applied to organosilicon chemistry industrial many necks today as catalyst the most frequently used in hydrosilylation
Domain, although such a catalyst relatively before catalyst compare, have higher catalytic efficiency, there is also storage is unstable simultaneously
It is fixed, reaction easily is produced with the heavy metal ion in storage condition and other active compounds, it is unstable to form new high-valence state
Fixed platinum compounds, platinum black precipitation is ultimately formed, loses catalytic activity.Therefore, develop one kind can with industrialized production, and
Can just it be particularly important in the potential new catalyst containing the environment stored for extended periods that can make catalyst poisoning ion.
The content of the invention
To solve the shortcomings that prior art and weak point, primary and foremost purpose of the invention is to provide a kind of storage-stable
Platiniferous hydrosilylation catalyst.
Another object of the present invention is to provide the preparation method of above-mentioned storage-stable platiniferous hydrosilylation catalyst.
The object of the invention is achieved through the following technical solutions：
A kind of storage-stable platiniferous hydrosilylation catalyst, the catalyst pass through compound containing platinum and organosilicon containing double bond
Oxygen alkyl ligand reacts, and adding a certain amount of organic compound after formation metal platinum-organic complex is prepared；It is wherein described to have
Machine compound is the compound with structure shown in formula I：
N is 4~10 in formula, preferably 5~7, more preferably 5；R is the alkane chain of carbon number 1~17, preferably carbon atom
Number is 4 alkane chain.
A kind of preparation method of storage-stable platiniferous hydrosilylation catalyst, comprises the following steps：
(1) compound containing platinum, silicone compounds containing unsaturated bond and sodium acid carbonate are dissolved in organic solvent, Ran Hou
Reacted 1~8 hour in 50 DEG C~120 DEG C under stirring；
(2) organic compound of the structural formula as shown in formula I is added after thing to be mixed fully reacts, and keeps 50 DEG C~120
Stop heating and stirring, natural cooling after DEG C stirring reaction certain time；Wherein, the organic compound and compound containing platinum of addition
The ratio between the amount of material be 1:1~30:1；
(3) reaction solution is transferred out from container, then sodium acid carbonate separated from reaction solution；It will get rid of
Organic solvent in the reaction solution of sodium acid carbonate is separated, that is, obtains the concentration of storage-stable platiniferous hydrosilylation catalyst
Liquid, used using hydrosilylation catalyst can be worked as after vinyl silicone oil or organic solvent in certain ratio dilution.
Step (1) described compound containing platinum includes H2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4In extremely
Few one kind.Preferably, using H2PtCl6With Pt (COD)2At least one of.
Step (1) described organic solvent can select dichloromethane, chloroform, dichloroethanes, acetonitrile, tetrahydrofuran,
At least one of conventional organic solvent such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE.It is excellent
Selection of land, use at least one of chloroform or dichloromethane.
The ratio of the amount of the material of step (1) sodium acid carbonate and compound containing platinum is 1:1~8:1.
Silicone compounds containing unsaturated bond described in step (1) are tetramethyl divinyl disiloxane or tetramethyl tetrem
Alkenyl cyclotetrasiloxane.
The amount ratio of step (1) compound containing platinum and the material of the silicone compounds containing unsaturated bond is 1:2~1:
10, preferably 1:4.
Step (1) heat time is preferably 3 hours, and heating-up temperature is preferably 70 DEG C~90 DEG C.
The structural formula of step (2) described organic compound is as shown in formula I；The chemical constitution of the organic compound is preferably
N is equal to 5, R C4H9。
The time of step (2) described stirring reaction is 15~100 minutes, preferably 30 minutes.
The ratio between amount of material of step (2) organic compound and compound containing platinum is preferably 4:1~16:1, more preferably
For 12:1.
Compared with prior art, the present invention has advantages below and beneficial effect：
Storage-stable platiniferous hydrosilylation catalyst provided by the invention, solves existing platiniferous Si―H addition reaction catalysis
Agent storage is unstable, is easily reacted with metal ion and other active compounds, the problem of losing catalytic activity.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
1g chloroplatinic acids, 2g tetramethyl divinyl disiloxanes, 0.4g sodium acid carbonate and 30mL chloroform are added
Enter into 50mL two mouthfuls of flasks, 80 DEG C of agitating and heatings are reacted 2 hours；Then add n in structural formula shown in 28g formulas I and be equal to 5, R
Equal to C4H9Organic compound, kept for 80 DEG C, continue heating stirring 30 minutes, after stopping reaction, question response liquid natural cooling
Afterwards, the sodium acid carbonate in reaction solution is filtered out using filter paper.Chloroform in filtrate is separated using the mode of vacuum distillation
Go out, obtain the concentrate of catalyst, concentrate is diluted to finite concentration using toluene, you can as hydrosilylation catalyst
Use.
Embodiment 2
By 1g chloroplatinic acids, 4g tetramethyl divinyl disiloxane, 0.8g sodium acid carbonate and 30mL dichloromethane
It is added in 50mL two mouthfuls of flasks, 60 DEG C of agitating and heatings are reacted 3 hours；Then n in structural formula shown in 30g formulas I is added to be equal to
6th, R C3H7Organic compound, keep 60 DEG C continue react 30min, stop reaction after, after question response liquid natural cooling, use
The method of centrifugation separates the sodium acid carbonate in reaction solution.It is using the method for vacuum distillation that the dichloromethane in reaction solution is whole
Separate, obtain the concentrate of catalyst, concentrate is diluted to finite concentration using vinyl silicone oil, you can as silicon hydrogen
Addition catalyst uses.
Embodiment 3
By 1g Pt (COD)2, 4g t etram-ethyltetravinylcyclotetrasiloxane, 1g sodium carbonate and 30mL chloroform
It is added in 50mL two mouthfuls of flasks, 70 DEG C of agitating and heatings are reacted 3 hours；Then n in structural formula shown in 27g formulas I is added to be equal to
5th, R is equal to CH3Organic compound, kept for 70 DEG C continue heating stirring 15 minutes, after stopping reaction, question response liquid natural cooling
Afterwards, the sodium acid carbonate in reaction solution is filtered out using filter paper.It is using the method for vacuum distillation that the chloroform in mixed liquor is complete
Portion separates, and obtains the concentrate of catalyst, concentrate is diluted into finite concentration using vinyl silicone oil, you can as silicon
Hydrogen addition catalyst uses.
Embodiment 4
By 1g chloroplatinic acids, 4g tetramethyl divinyl disiloxane, 0.6g sodium acid carbonate and 30mL dichloromethane
It is added in 50mL two mouthfuls of flasks, 80 DEG C of agitating and heatings are reacted 4 hours；Then n in structural formula shown in 35g formulas I is added to be equal to
7th, R is equal to CH3Organic compound, kept for 80 DEG C continue heating stirrings and reacted 25 minutes, after stopping reaction, question response liquid is natural
After cooling, the sodium acid carbonate in reaction solution is isolated using the method for centrifugation.Using the method for vacuum distillation by mixed liquor
Dichloromethane is totally separated out, obtains the concentrate of catalyst, and concentrate is diluted into finite concentration using toluene, you can is made
Used for hydrosilylation catalyst.
The catalyst that will be prepared in embodiment 1-4, it is added to the silicone oil that hydrogen content is 1% and the second that double bond content is 2%
In alkenyl silicone oil, the hardening time under test different temperatures, under the same conditions, same amount of catalyst, embodiment 1-4 are added
The hardening time of the catalyst of preparation is basically identical, it was demonstrated that catalytic activity does not have compared with traditional Karstedt catalyst
Obvious to reduce, specific data are as shown in table 1 to table 4：
The hardening time of catalyst prepared by the embodiment 1-4 of table 1 and traditional Karstedt catalyst
The hardening time of catalyst prepared by the embodiment 1-4 of table 2 and traditional Karstedt catalyst
The hardening time of catalyst prepared by the embodiment 1-4 of table 3 and traditional Karstedt catalyst
The hardening time of catalyst prepared by the embodiment 1-4 of table 4 and traditional Karstedt catalyst
The catalyst prepared in embodiment 1-4 and Karstedt catalyst are used to the percentage by weight 1% of vinyl
Vinyl silicone oil be diluted to 3000ppm, place in a reservoir, add the 30ppm compound for easily making catalyst poisoning, see
Examine storage time, platinum black occur in catalyst is defined, it is possible to find, embodiment 1-4 catalyst under the same conditions, storage it is steady
Fix time and be considerably longer than Karstedt catalyst, it is specific as shown in table 5.
The storage time of catalyst prepared by the embodiment 1-4 of table 5 and traditional Karstedt catalyst
| Karstedt | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Iron chloride | 3 days | ＞ 30 days | ＞ 30 days | ＞ 30 days | ＞ 30 days |
| Copper chloride | 5 days | ＞ 30 days | ＞ 30 days | ＞ 30 days | ＞ 30 days |
| Stannic chloride | 1 day | 15 days | 16 days | 20 days | 20 days |
| Stearylmercaptan | 1 day | 8 days | 8 days | 16 days | 20 days |
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of storage-stable platiniferous hydrosilylation catalyst, it is characterised in that the catalyst is by compound containing platinum and contains
Double bond organosiloxane ligand reaction, addition organic compound is prepared after forming metal platinum-organic complex；It is wherein described
Organic compound is the compound with structure shown in formula I：
N is 4~10 in formula；R is the alkane chain of carbon number 1~17.
2. storage-stable platiniferous hydrosilylation catalyst according to claim 1, it is characterised in that the n in formula I is 5
~7, R are the alkane chain that carbon number is 4.
3. the preparation method of the storage-stable platiniferous hydrosilylation catalyst described in claim 1 or 2, it is characterised in that bag
Include following steps：
(1) compound containing platinum, organosilicone compounds containing double bond and sodium acid carbonate are dissolved in organic solvent, then stirred
Reacted 1~8 hour in 50 DEG C~120 DEG C under state；
(2) organic compound of the structural formula as shown in formula I is added after thing to be mixed fully reacts, and is kept for 50 DEG C~120 DEG C and stirred
Stop heating and stirring, natural cooling after mixing reaction certain time；Wherein, the thing of the organic compound of addition and compound containing platinum
The ratio between amount of matter is 1:1~30:1；
(3) sodium acid carbonate and organic solvent in reaction solution are separated, that is, obtains storage-stable platiniferous hydrosilylation catalyst
Concentrate.
4. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly (1) described compound containing platinum includes H2PtCl6、PtCl2、Pt(COD)2、Na2PtCl4、K2PtCl4At least one of.
5. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly (1) described organic solvent be dichloromethane, chloroform, dichloroethanes, acetonitrile, tetrahydrofuran, N,N-dimethylformamide,
At least one of DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE.
6. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly the ratio of the amount of the material of (1) described sodium acid carbonate and compound containing platinum is 1:1~8:1.
7. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly organosilicone compounds containing double bond described in (1) are tetramethyl divinyl disiloxane or the silicon of tetramethyl tetravinyl ring four
Oxygen alkane.
8. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly the amount ratio of (1) described compound containing platinum and the material of the organosilicone compounds containing double bond is 1:2~1:10.
9. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that step
Suddenly the time of (2) described stirring reaction is 15~100 minutes.
10. the preparation method of storage-stable platiniferous hydrosilylation catalyst according to claim 3, it is characterised in that
The ratio between amount of material of step (2) organic compound and compound containing platinum is 4:1~16:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016101212124 | 2016-03-03 | ||
| CN201610121212 | 2016-03-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105854945A CN105854945A (en) | 2016-08-17 |
| CN105854945B true CN105854945B (en) | 2018-03-20 |
Family
ID=56636570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610221439.6A Active CN105854945B (en) | 2016-03-03 | 2016-04-11 | A kind of storage-stable platiniferous hydrosilylation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854945B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105797775B (en) * | 2016-03-23 | 2018-12-07 | 安徽正洁高新材料股份有限公司 | The preparation method of hydrosilylation vinyl platinum catalyst |
| CN106432734B (en) * | 2016-10-17 | 2019-07-12 | 东莞市贝特利新材料有限公司 | The preparation method of platinum catalyst, preparation method and silicon rubber |
| CN110252411B (en) * | 2019-06-26 | 2022-02-08 | 江西蓝星星火有机硅有限公司 | Complex platinum catalyst for producing epoxy-terminated silicone oil and preparation method and application thereof |
| CN113499800A (en) * | 2021-06-24 | 2021-10-15 | 江苏斯迪克新材料科技股份有限公司 | Karstedt catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518555A (en) * | 2001-06-07 | 2004-08-04 | ���ǻ�ѧ��˾ | Method for preparing metallic carbene-based catalysts for hyolrosilylation of unsaturated compounds and resulting catalysts |
| CN103687865A (en) * | 2011-08-01 | 2014-03-26 | 优美科股份公司及两合公司 | Method for preparation of platinum-carbonyl-siloxane compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2750349B1 (en) * | 1996-06-28 | 1998-10-16 | Rhone Poulenc Chimie | USE OF PLATINUM COMPLEXES IN PARTICULAR AS HOMOGENEOUS AND THERMOACTIVABLE HYDROSILYLATION CATALYSTS |
-
2016
- 2016-04-11 CN CN201610221439.6A patent/CN105854945B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518555A (en) * | 2001-06-07 | 2004-08-04 | ���ǻ�ѧ��˾ | Method for preparing metallic carbene-based catalysts for hyolrosilylation of unsaturated compounds and resulting catalysts |
| CN103687865A (en) * | 2011-08-01 | 2014-03-26 | 优美科股份公司及两合公司 | Method for preparation of platinum-carbonyl-siloxane compounds |
Non-Patent Citations (3)
| Title |
|---|
| 三芳基膦配体促进Karstedt催化剂催化硅氢加成反应研究;薛梅 等;《杭州师范大学学报（自然科学版）》;20140131;第13卷(第1期);第1-5页 * |
| 基于柱芳烃的有机功能材料;夏梦婵 等;《超分子化学专辑》;20150127;第27卷(第6期);第655-665页 * |
| 柱[5]芳烃衍生物的合成及其选择性键合行为的研究;舒晓燕;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20130215(第02期);第B014-22页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105854945A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105854945B (en) | A kind of storage-stable platiniferous hydrosilylation catalyst and preparation method thereof | |
| CN102977377B (en) | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent | |
| JP4351058B2 (en) | Alkene-platinum-silyl complex | |
| CN106432728B (en) | A kind of pheiiyldimetliyl siloxy cage-type silsesquioxane silicone rubber crosslinking agent and preparation method thereof | |
| CN105854946B (en) | A kind of platiniferous hydrosilylation catalyst and preparation method thereof | |
| CN101501047B (en) | Novel epoxy compound and process for production thereof | |
| JP2017533179A (en) | Platinum complexes and their use in compounds crosslinkable by hydrosilylation reactions | |
| EP3071585B1 (en) | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| CN110494440A (en) | Siloxanes is prepared in the presence of cationic silicon (II) compound | |
| CN109999905A (en) | A kind of preparation and application of highly selective hydrosilylation catalyst | |
| CN106519237A (en) | Diphenyl siloxy polyhedral oligomeric silsesquioxane silicone rubber cross-linking agent and preparation method thereof | |
| CN109867789A (en) | A kind of compatilizer and preparation method thereof improving ethylene propylene diene rubber and silicon rubber comixing compatibility | |
| CN104995200B (en) | By the hydrosilylation method of the light-catalysed siloxanes of polyoxometallic acid radical compound | |
| do Carmo et al. | Ferrocene adsorbed into the porous octakis (hydridodimethylsiloxy) silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination | |
| CN107497140B (en) | A kind of high efficiency defoaming agent and preparation method thereof | |
| JP2022531804A (en) | Preparation of siloxane in the presence of cationic germanium (II) compound | |
| CN106750306A (en) | A kind of pheiiyldimetliyl siloxy cage-type silsesquioxane silicone rubber crosslinking agent and preparation method thereof | |
| JP5368055B2 (en) | Process for producing silylated cage silicic acid, silylated cage silicic acid and polyhedral polysiloxane modified product obtained therefrom | |
| EP2935286B1 (en) | Hydrosilylation method | |
| CN102633829B (en) | Method for preparing amino siloxane | |
| CN107177037A (en) | A kind of acetylenic glycols ethoxylate is modified bola types organosiloxane and preparation method | |
| CN113577837A (en) | Organic silicon composition | |
| CN105153754B (en) | A kind of method of modifying of nano zine oxide inorganic powder material | |
| CN113402562B (en) | Preparation method and application of platinum complex | |
| WO2019044793A1 (en) | Method for manufacturing silsesquioxane compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221206 Address after: 512400 No.3 complex building, Ping'an 1st Road, Dongguan Dalingshan (Nanxiong) industrial transfer industrial park, Nanxiong City, Shaoguan City, Guangdong Province Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Patentee after: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee after: GUANGDONG GUANHAO HIGH-TECH CO.,LTD. Address before: 512400 Zhuji Industrial Park, Nanxiong City, Shaoguan City, Guangdong Province (Nanxiong Fine Chemical Base, Guangdong Province) Patentee before: NANXIONG MATERIAL PRODUCTION BASE OF CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICAL Co.,Ltd. Patentee before: GUANGZHOU CHEMISTRY Co.,Ltd. CHINESE ACADEMY OF SCIENCES Patentee before: GUANGDONG GUANHAO HIGH-TECH CO.,LTD. |